Alexey S. Kashin

• PhD
• Senior Researcher at N.D. Zelinsky Institute of Organic Chemistry

The great impact of the nanoscale organization of reactive species on their performance in chemical transformations creates the possibility of fine-tuning of reaction parameters by modulating the nano-level properties. This methodology is extensively applied for the catalysts development whereas nanostructured reactants represent the practically un...

Developments in chemistry, materials science and biology have been fuelled by our search for structure–property relationships in matter at different levels of organization. Transformations in chemical synthesis and living systems predominantly take place in solution, such that many efforts have focused on studying nanoscale systems in the liquid ph...

The development of approaches for creation of adaptive and stimuli-responsive chemical systems is particularly important for chemistry, materials science, and biotechnology. The understanding of response mechanisms for various external forces is highly demanded for the rational design of task-specific systems. Here, we report direct liquid-phase sc...

Real‐time field‐emission scanning electron microscopy (FE‐SEM) measurements and neural network analysis were successfully merged to observe the temperature‐induced behavior of soft liquid microdomains in mixtures of different ionic liquids with water. The combination of liquid FE‐SEM and in situ heating techniques revealed temperature‐driven soluti...

In this work, using a combination of scanning and transmission electron microscopy (SEM and TEM), the transformations of palladium‐containing species in imidazolium ionic liquids in reaction mixtures of the Mizoroki‐Heck reaction and in related organic media are studied to understand a challenging question of the relative reactivity of organic hali...

Protic imidazolium ionic liquids (PILs) have shown great potential as regents and catalysts in liquid-phase chemistry. However, their biological activity/toxicity and solvation properties are rather understudied compared to those of more common aprotic ionic liquids (APILs). In this work, for the first time, we studied the cytotoxicity of nine chem...

In the highlighted article, the effect of alkane and water additives on the structure of several ionic liquids was used to increase the acidity of liquid reaction media and to accelerate the acid-catalyzed transformations. A possible connection between the appearance of a pronounced microstructure of the obtained systems and their performance in ca...

Comprehensive studies dedicated to the search for specific properties of matter at the micro‐ and nanoscales have greatly enriched the fields of chemistry and materials science. From the point of view of synthetic chemistry, discoveries in the field of nanoscale catalysis, in which the size effects of active centers are used to accelerate the react...

In this chapter, we discuss the nature of nanoparticle catalysts and the mechanistic pathways of catalytic transformations. Evolution of catalytic centers involves a number of dynamic processes taking place in reaction mixtures during catalytic reactions. We briefly discuss applications of electron microscopy, mass spectrometry, DFT calculations, m...

A new family of protic ammonium ionic liquids (ILs) with various inorganic anions was synthesized from bio-derived 5-HMF. Starting with cellulose biomass, a complete preservation of the C6 unit was achieved throughout the synthetic sequence (no carbon loss). Evaluation of green metrics showed a significant advantage of the developed bio-derived pat...

The present article describes a conceptual view on the design of reusable bioderived high-value-added materials. The translation of a highly complex irregular structure of natural biopolymer into a well-defined hierarchically organized molecular chain led to the discovery of unique adhesive properties enhanced by a novel multiple binding effect. Fo...

In this work, the transfer of the flexible and easily tunable hierarchical structure of nickel organochalcogenides to different binary Ni-based nanomaterials via selective coupling of organic units was developed. We suggested the use of substituted aryl groups in organosulfur ligands (SAr) as traceless structure-inducing units to prepare nanostruct...

The ability to distinguish molecular catalysis from nanoscale catalysis provides a key to success in the field of catalyst development, particularly for the transition to sustainable economies. Complex evolution of catalyst precursors, facilitated by dynamic interconversions and leaching, makes the identification of catalytically active forms an in...

An efficient method for preparation of secondary amides from primary amides and aldehydes using rhodium on carbon matrix as catalyst was developed. The method does not require any external hydrogen source and carbon monoxide is used as a reducing agent. The most active rhodium catalysts were characterized by BET, TEM and XPS techniques. Unexpectedl...

During the last decades, micro-structuring phenomena, formation of polar domains and assembling of nano-scale heterogeneities in ionic liquids (ILs) have been discovered. Here we assess the influence of structuring effects in solution on biological activity of ionic systems. In the present work, we studied cytotoxicity of aqueous solutions of binar...

A catalytic system based on OX-1 metal-organic framework nanosheets is reported, incorporating catalytically active palladium (Pd) species. The Pd@OX-1 guest@host system is rapidly synthesised via a facile single-pot supramolecular assembly method, with the possibility of controlling the Pd loading. The structures of the re-sulting framework and of...

Fast and Convenient Method For FE-SEM Characterization of Microstructured Organic Solutions in Ionic Liquids - Volume 25 Issue S1 - Alexey S. Kashin, Valentine P. Ananikov

Until recently, chemical derivatives of platinum group metals have not been in a systematic direct contact with living organisms. The situation has changed dramatically due to anthropogenic activity, which has led to significant redistribution of these metals in the biosphere. Millions of modern cars are equipped with automotive catalytic converter...

R–NHC coupling was previously considered as a process of degradation of M/NHC species, however recent studies have pointed out that it may be responsible for generation of catalytically active NHC-free complexes or/and metallic nanoparticles. Therefore, a detailed and systematic study of R-NHC coupling for various carbene ligands is an important to...

Numerous reactions are catalyzed by complexes of metals (M) with N-heterocyclic carbene (NHC) ligands, typically in the presence of oxygen bases, which significantly shape the performance. It is generally accepted that bases are required for either substrate activation (exemplified by transmetallation in the Suzuki cross-coupling), or HX capture (e...

Inorganic and organic “solvent-in-salt” (SIS) systems have been known for decades but have attracted significant attention only recently. Molten salt hydrates/solvates have been successfully employed as non-flammable, benign electrolytes in rechargeable lithium-ion batteries leading to a revolution in battery development and design. SIS with organi...

The synthesis of bioplastic from plants and its use in a 3D printing process are reported by V. P. Ananikov et al. in their Communication (DOI: 10.1002/anie.201708528). Biomass-derived, easily accessible poly(ethylene-2,5-furandicarboxylate) was used for fused deposition modeling 3D printing. The suggested approach extends additive manufacturing pr...

Die Synthese von Bioplastik aus Pflanzen und dessen Verwendung in einem 3D-Druckprozess wird von V. P. Ananikov et al. in ihrer Zuschrift (DOI: 10.1002/ange.201708528) vorgestellt. Aus Biomasse gewonnenes, leicht zugängliches Poly(ethylen-2,5-furandicarboxylat) wurde zum 3D-Schmelzschichtdrucken verwendet. Der vorgeschlagene Ansatz erweitert additi...

Storage and handling of toxic wastes is a top-priority challenge for sustainable development and public health. In recent years, the risk of irreversible environmental pollution has been increasing gradually, necessitating the development of new concepts in this highly demanding area. Here, we report a flexible approach to address the problem using...

We demonstrate the utility of 100% biomass-derived poly(ethylene-2,5-furandicarboxylate) (PEF) as an efficient material for Fused Deposition Modeling (FDM) 3D printing. A complete cycle from cellulose to printed object has been performed. PEF-printed objects created in the present study demonstrated higher chemical resistance than objects printed w...

We demonstrate the utility of 100% biomass-derived poly(ethylene-2,5-furandicarboxylate) (PEF) as an efficient material for Fused Deposition Modeling (FDM) 3D printing. A complete cycle from cellulose to printed object has been performed. PEF-printed objects created in the present study demonstrated higher chemical resistance than objects printed w...

For the first time, extraction process in ionic liquids was visualized by direct electron microscopy observation. Microscopy images revealed the micro-heterogeneous nature of the studied extraction systems. Depending on the nature of ionic liquids and studied compounds, four main micro-scale areas were observed: a) uniform homogeneous phase; b) mic...

The direct vinylation of an OH group in alcohols and phenols was carried out utilizing a novel CaC2/KF solid acetylene reagent in a simple K2CO3/KOH/DMSO system. The functionalization of a series of hydroxyl-group-containing substrates and the post-modification of biologically active molecules were successfully performed using standard laboratory e...

Metal complexes bearing N-heterocyclic carbene (NHC) ligands are typically considered the system of choice for homogeneous catalysis with well-defined molecular active species due to their stable metal–ligand framework. A detailed study involving 19 different Pd-NHC complexes with imidazolium, benzimidazolium, and triazolium ligands has been carrie...

Electron microscopy, which has become a routine tool of materials science, heterogeneous catalysis, metallurgy and some other areas, is currently attracting increasing attention of researchers working in the area of fine organic synthesis. The modern capabilities for direct visualization of micro- and nano-objects suitable for characterization of e...

Copper-oxide-catalyzed cross-coupling reaction is a well-known strategy in heterogeneous catalysis. A large number of applications have been developed, and catalytic cycles have been proposed based on the involvement of the copper oxide surface. In the present work, we have demonstrated that copper(I) and copper(II) oxides served as precursors in t...

Water-containing organic solutions are widespread reaction media in organic synthesis and catalysis. This type of multicomponent liquid system has a number of unique properties because of the tendency for water to self-organize in mixtures with other liquids. The characterization of these water domains is a challenging task because of their soft an...

The liquid-phase hydrogenation of diphenylacetylene over Pd catalysts supported on Al2O3 with different specific surface areas has been investigated. A decrease in the specific surface area of the support leads to a marked increase in the selectivity of the reaction. The observed increase in the selectivity is due to the increase in the size of Pd0...

Gaining insight into Pd/C catalytic systems aimed at locating reactive centers on carbon surfaces, revealing their properties and estimating the number of reactive centers presents a challenging problem. In the present study state-of-the-art experimental techniques involving ultra high resolution SEM/STEM microscopy (1 Å resolution), high brillianc...

In situ generated catalysts and preformed catalysts are two practical strategies widely used in cross-coupling methodology that have long been considered to involve the same active species in the catalytic cycle. Recent mechanistic studies have revealed two fundamentally different pictures of catalytic reactions in solution. Preformed catalysts wit...

A new approach for the catalytic carbon–sulfur bond formation via cross-coupling reaction is reported. For the first time nano-structured nickel organosulfides [Ni(SAr)2]n were used as a source of SAr groups in catalytic cross-coupling reaction. A unique effect of morphology control of the reactivity of SAr groups in cross-coupling reaction was fou...

Semihydrogenation of acetylenes is intensively studied within the last years due to large industrial and academic relevance of its products. In this study a selective semihydrogenation of diphenylacetylene to corresponding alkenes was used as a model reaction to reveal effects of the second element on the performance of bimetallic Pd M catalysts. A...

In the present review we describe the emerging tendency for creating target-oriented analytical approaches designed to solve important chemical tasks by using a combination of analytical tools. The concept is illustrated by selected examples of advances of NMR spectroscopy, mass spectrometry and electron microscopy in the analysis and study of gas-...

Soluble gold pre-catalysts, aimed for homogeneous catalysis, under certain conditions may form nanoparticles, which dramatically change the mechanism and initiate different chemistry. The present study addresses the question of designing of gold catalysts taking into account possible interconversions and contamination at the homogeneous/heterogeneo...

In situ generated catalysts and preformed catalysts are two practical strategies widely used in cross-coupling methodology that have long been considered to involve the same active species in the catalytic cycle. Recent mechanistic studies have revealed two fundamentally different pictures of catalytic reactions in solution. Preformed catalysts wit...

In situ generated catalysts and preformed catalysts are two practical strategies widely used in cross-coupling methodology that have long been considered to involve the same active species in the catalytic cycle. Recent mechanistic studies have revealed two fundamentally different pictures of catalytic reactions in solution. Preformed catalysts wit...

Magnetron sputtering was successfully used to obtain nanosized metal films and metal nanoparticles, which can be useful for development of novel methods in organic chemistry. The morphology of the nanosized (5-100 nm) objects obtained was examined by SEM. The pattern of dependence of the morphology and size of the nanosized objects on the nature of...

The first practical procedure is reported for the synthesis of (E,E)-1,4-diiodobuta-1,3-diene from very simple starting materials (acetylene and I(2)). A pure crystalline product was obtained in a green chemical procedure utilizing the key advantages of highly selective Pt-catalyzed transformation and 100% atom efficiency of the addition reaction....

It is shown that meso-substituted polymethine dyes are promising spectral and fluorescent probes for biomacromolecules. Some dyes are recommended for application in real biological objects and were used for analysis of extracellular media of the eye.

The noncovalent interaction of two anionic cyanine dyes with human and bovine serum albumins was studied by spectral and fluorescent methods. Upon the interaction with albumins, a growth of fluorescence and, in most cases, a long-wavelength shift of the dye absorption band are observed. For the meso-substituted cyanine dye 3,3′-di-(γ-sulfopropyl)-9...

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The acid-catalyzed oxidation of cycloalkanones C5–C8 and C12 with hydrogen peroxide in alcohols was performed, and dicarboxylic acid esters were obtained as the major products in 53–70% yields. In the first step, geminal bishydroperoxides are generated from five-to-seven-membered cyclic ketones. The Baeyer–Villiger reaction is a side process accomp...